WO2005073348A1 - 炭化水素油の脱硫方法 - Google Patents

炭化水素油の脱硫方法 Download PDF

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Publication number
WO2005073348A1
WO2005073348A1 PCT/JP2005/001065 JP2005001065W WO2005073348A1 WO 2005073348 A1 WO2005073348 A1 WO 2005073348A1 JP 2005001065 W JP2005001065 W JP 2005001065W WO 2005073348 A1 WO2005073348 A1 WO 2005073348A1
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Prior art keywords
sulfur
content
mass
less
hydrocarbon oil
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PCT/JP2005/001065
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English (en)
French (fr)
Japanese (ja)
Inventor
Yasuhiro Toida
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Japan Energy Corporation
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Application filed by Japan Energy Corporation filed Critical Japan Energy Corporation
Priority to JP2005517474A priority Critical patent/JP5252674B2/ja
Priority to EP20050709370 priority patent/EP1715025A4/de
Priority to CN2005800037575A priority patent/CN1914298B/zh
Priority to US10/586,606 priority patent/US8021540B2/en
Priority to CA2553713A priority patent/CA2553713C/en
Publication of WO2005073348A1 publication Critical patent/WO2005073348A1/ja
Priority to NO20063884A priority patent/NO20063884L/no
Priority to KR1020067017844A priority patent/KR101176233B1/ko

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel

Definitions

  • the present invention relates to a hydrocarbon oil, in particular, an aromatic hydrocarbon oil such as benzene, toluene, xylene, naphthalene, methyl naphthalene, and dimethyl naphthalene, or a hydrocarbon oil containing the aromatic hydrocarbon, or kerosene. It relates to a desulfurization method for light oil and the like.
  • Aromatic hydrocarbons such as benzenes and naphthalenes each contain sulfur compounds as impurities as the power obtained by separation from petroleum and coal tar. These aromatic hydrocarbons are used as a base material for various petrochemical products or intermediate raw materials. When producing these products or intermediate raw materials, sulfur compounds become catalyst poisons, so lppm or less, preferably 0.5 ppm or less. It is often necessary to desulfurize to less than ppm, more preferably to less than 0.1 ppm. However, the sulfur compounds contained in these aromatic hydrocarbons are aromatic sulfur compounds such as thiophenes, benzothiophenes, and dibenzothiophenes, which have similar boiling points and other properties. Precise separation by distillation is not easy.
  • Patent Document 1 A method of adsorbing and removing sulfur compounds with a physical adsorbent that does not involve a reaction (see Patent Document 1) has been studied, but it is easy to adsorb and remove sulfur compounds contained in hydrocarbon oils having a high aromatic content. It is particularly difficult when the concentration of the sulfur compound is low.
  • Patent Document 2 A method of adsorbing and removing sulfur compounds as sulfur with a chemical adsorbent that involves a reaction (see Patent Document 2) has also been studied. This is a study on naphtha having a low aromatic content. Thiophenes and benzothiophenes. Dibenzothiophenes are mentioned, and they are.
  • the desulfurization reaction by hydrorefining is a reaction that uses hydrogen at high temperatures and high pressures, so it is not only a problem of high operating costs and equipment costs, but aromatic hydrocarbons themselves are hydrogenated and decomposed to generate impurities. In particular, when the concentration of the sulfur compound is low, the generation of impurities becomes remarkable.
  • Oxidative desulfurization using an oxidizing agent involves the use of an oxidizing agent such as hydrogen peroxide or an acid catalyst and requires phase separation, which complicates the equipment and reduces operating and equipment costs. There is a problem of high.
  • Patent Literatures 3 and 4 There is also known a method of removing sulfur compounds by homopolymerization or decomposition by adding anhydrous aluminum chloride. If the desulfurization rate is low, there is a problem.
  • Patent Document 1 Japanese Patent Application No. 2003-77594
  • Patent Document 2 JP-A-2-132186
  • Patent Document 3 Japanese Patent Publication No. 47-47021
  • Patent Document 4 JP-A-63-57539
  • the present inventors have arrived at the present invention capable of effectively removing organic sulfur compounds, particularly, to lppm or less as sulfur. That is, the present invention relates to a hydrocarbon oil containing at least one sulfur compound selected from the group consisting of thiophenes, benzothiophenes and dibenzothiophenes, or a hydrocarbon oil further containing an aromatic hydrocarbon. And a solid acid catalyst and / or an activated carbon loaded with a transition metal oxide.
  • desulfurization is preferably performed by contacting a hydrocarbon oil with a solid acid catalyst to react sulfur compounds contained in the hydrocarbon oil and Z or sulfur compounds with an aromatic hydrocarbon. Maseru.
  • a sulfur compound in the hydrocarbon oil and a heavy sulfur compound generated by a reaction between the sulfur compounds contained in the hydrocarbon oil and / or the sulfur compound and the aromatic hydrocarbon are converted into a solid acid catalyst and / or a transition acid. It is preferable to adsorb the activated carbon on which the metal oxide is supported, and in particular, desulfurize the concentration of all sulfur compounds contained in the hydrocarbon oil to lppm or less as sulfur.
  • the solid acid catalyst used in the hydrocarbon oil desulfurization method of the present invention is preferably a proton type catalyst.
  • Faujasite-type zeolite zeolite selected from the group consisting of proton-type mordenite and proton-type ⁇ zeolite, more preferably, these zeolite has a silica / alumina ratio of 100 mol / mol or less; Further, these zeolites preferably have a cation content other than protons of 5% by mass or less.
  • the solid acid catalyst is preferably a catalyst composed of a solid superacid selected from the group consisting of sulfated zirconia, sulfated alumina, tin sulfated oxide, iron sulfated oxide, dinolecolate tungstate, and tin tungstate oxide. Those having a specific surface area of 100 m 2 / g or more are more preferable.
  • the transition metal oxide is preferably copper oxide.
  • the hydrocarbon oil used is preferably one containing an aromatic hydrocarbon as a main component.
  • the aromatic hydrocarbon may be benzene, alkylbenzene having 7 to 14 carbon atoms, naphthalene.
  • at least one aromatic hydrocarbon selected from the group consisting of alkylnaphthalenes having 11 to 18 carbon atoms contains the preferred aromatic hydrocarbon, so that the effects of the present invention can be enjoyed.
  • the desulfurization method of the present invention can be preferably used for hydrocarbon oils such as kerosene and light oil. Particularly, in a fuel cell vehicle using kerosene or light oil as an on-board reforming fuel, the desulfurization method of the present invention can be suitably used when desulfurizing the kerosene or light oil.
  • the present invention desulfurizes kerosene having a dibenzothiophene concentration of 0.1 ppm or less as sulfur using the above desulfurization method, and then supplies the fuel to a fuel cell system to supply hydrogen for fuel cells. It is a fuel cell system to generate.
  • the sulfur component is not more than ⁇ ppm, and the ratio of thiophenes, benzothiophenes and dibenzothiophenes to the total sulfur content is 10. Kerosene that is less than / ⁇ or kerosene in which the ratio of thiophenes and benzothiophenes to total sulfur is 10% or less.
  • the solid acid catalyst and / or the transition metal oxide are supported.
  • activated carbon a sulfur compound in a hydrocarbon oil or a heavier sulfur compound generated by a catalytic function such as a solid acid catalyst is supported by a solid acid catalyst and / or a transition metal oxide. Since sulfur is adsorbed on activated carbon and desulfurized, in particular, even sulfur compounds in aromatic hydrocarbon oil can be efficiently and economically removed. Therefore, according to the present invention, it is possible to provide a hydrocarbon oil containing particularly low sulfur content, kerosene or light oil, or an aromatic hydrocarbon such as benzenes and naphthalenes.
  • the sulfur compound since the sulfur compound is not made heavy by alkylating the sulfur compound in the desulfurization method of the present invention, the sulfur compound can be combined without using a special alkylating agent such as olefin.
  • a special alkylating agent such as olefin.
  • FIG. 1 is a graph showing the change over time in the sulfur content of kerosene that flowed out of a column when kerosene was passed through a column filled with sulfated dinoleconia and desulfurized.
  • a sulfur compound contained in a hydrocarbon oil can be efficiently reduced by a solid acid catalyst or activated carbon supporting a transition metal oxide. Can be removed.
  • Hydrocarbon oils to which the desulfurization method of the present invention can be suitably applied include alkylbenzenes having 7 to 14 carbon atoms such as benzene, toluene, and xylene; and carbon atoms having 11 to 18 carbon atoms such as naphthalene, methylnaphthalene, and dimethylnaphthalene.
  • Aromatic hydrocarbon oils containing alkylnaphthalenes as a main component, and particularly those containing benzene, toluene, xylene, naphthalene, methylnaphthalene, dimethylnaphthalene and the like as main components are preferable.
  • the content of the aromatic hydrocarbon is preferably 60% by mass or more, more preferably 80% by mass or more. Further, for example, the present invention can be applied to an aromatic hydrocarbon fraction before benzene, toluene, xylene and the like are isolated by precision distillation.
  • the desulfurization method of the present invention can also be used for desulfurization of paraffin-based hydrocarbons such as decane, kerosene and light oil.
  • paraffin-based hydrocarbons such as decane, kerosene and light oil.
  • the sulfur contained in the hydrocarbons is strictly removed as a poison of the reforming catalyst during the hydrogen production process. Need to leave.
  • the desulfurization method of the present invention can reduce sulfur compounds to extremely low concentrations, it can be particularly preferably used when kerosene or light oil is used as an on-board reforming fuel in a fuel cell vehicle.
  • kerosene having a sulfur concentration of 0.1 ppm or less as sulfur, which is difficult to remove, is used, desulfurization can be more easily performed by the desulfurization method of the present invention. Therefore, by incorporating the desulfurization method of the present invention into a fuel cell system, kerosene having a low concentration of dibenzothiophenes is used to produce hydrogen without poisoning a reforming catalyst for hydrogen production, and Can be supplied.
  • the fuel cell system incorporating the desulfurization method of the present invention may be a stationary type or a movable type (for example, a fuel cell vehicle).
  • Kerosene is an oil mainly composed of hydrocarbons having about 12 to 16 carbon atoms, having a density (15 ° C) of 0.790 0.80 g / cm 3 and a boiling point range of about 150 320 ° C. It contains a large amount of paraffinic hydrocarbons, but contains about 30% by volume of aromatic hydrocarbons and about 0.5% by volume of polycyclic aromatics. Generally, it is the No. 1 kerosene specified in Japanese Industrial Standards J IS K2203 as fuel for lighting and heating.
  • flash point 40 ° C or higher, 95% distillation temperature 270 ° C or lower, sulfur content 0.008 mass% or lower, smoke point 23mm or higher (for cold weather, 21mm or higher), copper plate corrosion (50 ° C or higher) C, 3 hours)
  • sulfur content is from several ppm to less than 80 ppm
  • nitrogen content is from several ppm to about 10 ppm.
  • the desulfurization method of the present invention has a more remarkable effect in removing thiophenes and benzothiophenes than dibenzothiophenes, and therefore, a hydrocarbon oil having a low content of dibenzothiophenes, especially light oil Kerosene can be used more preferably.
  • Dibenzothiophenes have a relatively high boiling point and may be removed by distillation or may be removed by other known methods.
  • Diesel oil is an oil mainly composed of hydrocarbons having about 16 to 20 carbon atoms, having a density (15 ° C) of 0.820 0.80 g / cm 3 and a boiling point range of about 140 390 ° C. It contains a large amount of paraffinic hydrocarbons, but also contains about 1030% by volume of aromatic hydrocarbons and about 110% by volume of polycyclic aromatics.
  • the sulfur content is from several ppm to less than 100 ppm, and the nitrogen content contains several ppm and several tens ppm.
  • the solid acid catalyst used in the present invention includes sulfur compounds in a hydrocarbon oil and Z or sulfur compounds. It catalyzes the reaction of yellow compounds with aromatic hydrocarbons (i.e., the reaction of thiophene and benzene rings) to promote the formation of heavy sulfur compounds and further promotes the formation of sulfur compounds in hydrocarbon oils, especially It also functions as an adsorbent for adsorbing heavy sulfur compounds.
  • the heavier sulfur compound in the present invention is a reaction between sulfur compounds or mainly between a thiophene ring and a benzene ring. Therefore, the sulfur compound contained in naphtha is converted into an alkylating agent (such as olefin). In this invention, a special alkylating agent such as olefin is not required.
  • solid acid catalyst examples include, in addition to solid acids such as zeolite, silica'alumina, and activated clay, sulfate zirconia, sulfate alumina, tin sulfate oxide, sulfate iron oxide, dinolecoure tungstate, Solid superacids such as tin tungstate oxide can also be mentioned.
  • solid acids such as zeolite, silica'alumina, and activated clay, sulfate zirconia, sulfate alumina, tin sulfate oxide, sulfate iron oxide, dinolecoure tungstate, Solid superacids such as tin tungstate oxide can also be mentioned.
  • the solid acid catalyst is preferably at least one zeolite selected from proton-type faujasite-type zeolites, proton-type mordenites and proton-type j3 zeolites.
  • the silica / alumina ratio is preferably 100 mol / mol or less, more preferably 30 mol / mol or less, because the smaller the silica / alumina ratio, the larger the amount of acid serving as an adsorption site.
  • Zeolite has the general formula: xM / nO -Al ⁇ -ySiO ⁇ ⁇ 0 (where ⁇ is the cation ⁇
  • valence is a number of 1 or less, y is a number of 2 or more, and z is a number of 0 or more) is a general term for crystalline hydrous aluminosilicate.
  • the structure of zeolite can be found on the home of the International Zeolite Association (I ZA) Structure Commission 1 ⁇ http://www.iza-structure.org/ etc. ⁇ or AIO tetrahedral structure is tertiary
  • charge compensation cations such as alkali metals and alkaline earth metals are held in pores and cavities.
  • the charge compensating cation can be easily exchanged for another cation such as a proton.
  • the acid treatment increases the Si ⁇ / Al O molar ratio and increases the acid strength.
  • the amount of solid acid decreases. Since the acid strength does not significantly affect the adsorption of sulfur compounds, it is preferable not to lower the amount of solid acid.
  • Faujasite-type zeolite has a structural unit having a four-membered ring, a six-membered ring and And a 6-membered double ring.
  • the micropore has a three-dimensional structure, the entrance is a circle formed by a non-planar 12-membered ring, and the crystal system is cubic.
  • Faujasite a natural zeolite of faujasite type, is represented by the molecular formula (Na, Ca, Mg) ⁇ ⁇ 1 Si ⁇ ⁇ 240 ⁇ ⁇
  • micropore diameter 7.4 X 7.4 mm and the unit cell size is 24.74 mm.
  • X-type and Y-type exist as faujasite-type synthetic zeolites.
  • NaX type zeolite is Na [(AIO)
  • NaY-type zeolites can adsorb molecules up to an effective diameter of about 8A.
  • the faujasite-type zeolite preferably used in the present invention has a general formula: xNa 0 -A1 ⁇ -ySiO
  • the content of cations other than protons such as sodium is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • Mordenite the structural units of the skeleton structure are a 4-membered ring, a 5-membered ring and an 8-membered ring.
  • micropores have a one-dimensional structure and a three-dimensional structure, the entrance is elliptical formed by non-planar 12-membered and 8-membered rings, and the crystal system is orthorhombic.
  • Mordenite which is a natural zeolite, includes mordenite, which has a molecular formula of NaAlSiO
  • Mordenite also exists as a synthetic zeolite. Na mordenite can adsorb molecules up to an effective diameter of about 7A. Moldenite preferably used in the present invention is represented by the general formula: xNa 0 -A1 O -ySiO, X ⁇ 1 and y ⁇ 100,
  • Si ⁇ / Al O molar ratio is lOOmol
  • / mol or less is preferred, especially 30 mol / mol or less, and further preferably 10 mol / mol or less.
  • the content of cations other than protons such as sodium is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • ⁇ zeolite In ⁇ zeolite ( ⁇ ⁇ ⁇ ), the structural units of the skeleton structure are a 4-membered ring, a 5-membered ring and a 6-membered ring.
  • Mi The micropore has a two-dimensional structure, the entrance is a circle formed by a non-planar 12-membered ring, and the crystal system is tetragonal.
  • Beta polymorph A is represented by the molecular formula Na
  • the micropore diameter is 6.6 X 6.7 A and 5.6 X 5.6 A, and the unit cell size force is 12.661 X 12.661 X 26.406 A.
  • the molar ratio of SiO / AlO is preferably 100 mol / mol or less.
  • the content of cations other than protons such as sodium is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • the charge-compensating cation of the zeolite used in the present invention is a proton, that is, hydrogen, and the content of cations other than protons such as sodium, potassium, magnesium, and calcium is preferably 5% by mass or less, more preferably 5% by mass or less. Is 3% by mass or less, more preferably 1% by mass or less.
  • the crystallinity is preferably 80% or more, particularly preferably 90% or more, and the crystallite diameter is preferably 5 ⁇ m or less, particularly preferably 1 ⁇ m or less.
  • the average particle size of 30 ⁇ ⁇ less, particularly 10 / im is the specific surface area gestures et preferred below 300 meters 2 / g or more on, especially 400 meters 2 / g or more.
  • a solid superacid catalyst is defined as a Hammett's acidity function H power S-11.93 of 100%
  • a catalyst consisting of a solid acid having an acid strength higher than that of sulfuric acid, such as a hydroxide or oxide of silicon, aluminum, titanium, zirconia, tungsten, molybdenum, iron, etc., or graphite, an ion exchange resin, etc.
  • sulfuric acid such as a hydroxide or oxide of silicon, aluminum, titanium, zirconia, tungsten, molybdenum, iron, etc., or graphite, an ion exchange resin, etc.
  • Sulfuric acid, antimony pentafluoride, tantalum pentafluoride, boron trifluoride, etc. attached to or supported on a carrier, dinoreconium oxide (Zr ⁇ ), oxidized
  • zirconium, alumina, tin oxide, sulfate zirconia obtained by treating iron oxide or titania with sulfuric acid, sulfate sulfate alumina, sulfate sulfate tin oxide, sulfate iron oxide, which were previously proposed by the present applicant. It is preferable to use sulphate titania, or dinorecouy tungstate or tin stannate oxide, which is obtained by kneading, mixing and firing a plurality of metal hydroxides and Z or hydrated oxides.
  • JP-B-59-6181, JP-B-59-40056, JP-A-04-187239, JP-A-04-187241 See Japanese Unexamined Patent Application Publication No. 2566814, Japanese Patent No. 2992972, Japanese Patent No. 3251313, Japanese Patent No. 3328438, Japanese Patent No. 3432694, Japanese Patent No. 3517696, Japanese Patent No. 3553878, and Japanese Patent No. 3568372.
  • the acid strength (H 2) refers to whether the acid point on the catalyst surface is
  • It is defined by the ability to receive an electron pair and is represented by a pKa value, and can be measured by a known indicator method or a gas base adsorption method.
  • the acid strength of a solid acid catalyst can be directly measured using an acid-base conversion indicator with a known pKa value.
  • p-nitrotoluene (pKa value; -11.4), m-nitrotoluene (pKa value; _12.0), p-nitrochlorobenzene (pKa value; -12.7), 2,4-dinitrotoluene (pKa value; -13.8), 2 , 4_dinitrofluorobenzene (pKa value; -14.5), 1,3,5-trichlorobenzene 1 ⁇ ⁇ value; _16.1), etc., immers the catalyst in a solution of cyclohexane or sulfuryl sulfuryl, When the discoloration of the indicator to acidic color is observed, it is the same or less than the pKa value at which the indicator discolors to acidic color.
  • the above-mentioned zeolite or solid superacid catalyst can be used as it is.
  • a molded article containing these zeolite or solid superacid catalyst in an amount of 30% by weight or more, particularly 60% by weight or more is preferably used.
  • the shape in order to increase the concentration gradient of the sulfur compound, in the case of a flow-through type, a small shape, particularly a spherical shape, is preferable as long as the pressure difference before and after the container filled with the desulfurizing agent does not increase.
  • the diameter is preferably 0.5 to 5 mm, particularly preferably 13 to 13 mm.
  • the diameter is preferably 0.1 to 4 mm, particularly preferably 0.1 to 2 mm, and the length is preferably 0.55 times, particularly 112 times the diameter.
  • the specific surface area of the solid acid catalyst including the case of the solid superacid catalyst, greatly affects the adsorption capacity of sulfur compounds
  • 100m 2 Zg or more is preferable, and 200m 2 / g or more is particularly preferable. It is preferably 300 m 2 Zg or more.
  • the pore volume having a pore diameter of 10 A or less is preferably 0.10 ml / g or more, particularly preferably 0.20 ml / g or more, in order to increase the adsorption capacity of the sulfur compound.
  • the pore volume of the pore diameter of 10 A or more and 0.1 xm or less is 0.05 mlZg or more, particularly 0.10 ml / g or more in order to increase the diffusion rate of the sulfur compound in the pores. It is preferable to do.
  • the pore volume having a pore diameter of 0.1 / m or more is preferably 0.3 ml / g or less, particularly preferably 0.25 ml / g or less, in order to increase the mechanical strength of the molded article.
  • the specific surface area and the total pore volume are measured by a nitrogen adsorption method, and the macropore volume is measured by a mercury intrusion method.
  • the nitrogen adsorption method is simple, commonly used, and has been described in various literatures. For example, Kazuhiro Washio: Shimadzu Review, 48 (1), 35-49 (1991), ASTM (.American Society for Testing and Materials) Standard est Method D 4365-95.
  • zeolite When zeolite is used as a molded product, as described in JP-A-4-198011, a semi-finished product may be molded and then dried and fired, or the zeolite powder may be used as needed. After mixing and forming a binder (binder), drying and baking may be performed.
  • binder binder
  • binder examples include clays such as alumina and smectite, and inorganic binders such as water glass. These binders may be used to the extent that they can be molded, and are not particularly limited, but are usually used in an amount of about 0.05 to 30% by weight based on the raw materials. Mixing inorganic particles such as silica, alumina, and other zeolites and organic substances such as activated carbon to improve the adsorption performance of sulfur compounds that are difficult to adsorb zeolite, and increasing the amount of mesopores and macropores to reduce sulfur The diffusion rate of the compound may be improved. Further, the adsorption performance may be improved by compounding with a metal.
  • the breaking strength of the carrier is not less than 3. Okg / pellet, especially not less than 3.5 kg / pellet. It is preferred.
  • the breaking strength is measured by a compression strength measuring instrument such as a Kiya tablet breaking strength measuring instrument (Toyama Sangyo Co., Ltd.).
  • the types of transition metal oxides used for the activated carbon carrying the transition metal oxide include silver, mercury, copper, cadmium, lead, molybdenum, zinc, cobalt, manganese, nickel, platinum, palladium, and iron.
  • Preferable are oxides of copper, zinc, and nickel from the viewpoints of safety and economy.
  • copper is inexpensive, and has excellent adsorption of sulfur compounds even in a wide temperature range from about room temperature to about 300 ° C, in the state of copper oxide which is not subjected to reduction treatment, and in the absence of hydrogen. It is particularly preferable because it shows performance.
  • Activated carbon used as a porous carrier is porous particles containing carbon as a main component.
  • the surface area is at least 500 m 2 / g, preferably at least 700 m 2 / g.
  • any of granular, fibrous, powder, and molded products can be used, it is preferable to use as activated carbon molded products.
  • the shape can be a granular shape, a honeycomb shape, a mat shape, a felt shape, or the like. Usually it is mainly amorphous with an average diameter of 0.8-1.7 mm. It is preferable that the breaking strength of the carrier is not less than 3.0 kgZ pellets, especially not less than 3.5 kgZ pellets, since cracking of the adsorbent does not occur.
  • the copper oxide-carrying activated carbon adsorbent preferably used supports a copper component.
  • the copper component is preferably contained in an amount of 0.1 to 30% by weight, particularly 10 to 20% by weight as a copper element weight based on the weight of the adsorbent. If necessary, components other than copper can be further supported. As a component other than copper, zinc or iron can be supported, but it is preferable that only copper is supported.
  • the transition metal contained in the adsorbent is preferably 70% by weight or more, particularly 95% by weight. % Or more is preferably a copper component.
  • the method of contacting the activated carbon carrying the solid acid catalyst or the transition metal oxide with the hydrocarbon oil may be a batch system (batch system) or a flow system, but the solid acid catalyst or the transition metal oxide carrier formed in a container is contacted.
  • a flow type in which activated carbon is filled and a hydrocarbon oil flows is more preferable.
  • the distribution type as a condition for contacting the pressure is atmospheric-pressure 50 kg / cm 2 G, is preferably Tsune ⁇ Ichi 10 kg / cm 2 G, particularly 0.1- 3kg / cm 2 G Shi favored ,.
  • the flow rate is 0.1-1 lOOhr in LHSV, especially 0.5-20hr- 1 .
  • the temperature at which the desulfurization treatment is performed is preferably slightly higher in the case of a solid acid catalyst because the sulfur compounds that generate heavy sulfur compounds and / or the reaction of the sulfur compounds with the aromatic hydrocarbons are involved. And particularly preferably 30-100 ° C. In the case of a transition metal oxide-supported activated carbon, no reaction can be expected, but since it is suitable for physical adsorption, a temperature of 150 ° C or lower, which is suitable for physical adsorption, is preferred.
  • the solid acid catalyst and the transition metal oxide-supported activated carbon may be used alone or in combination.
  • the reaction product of the solid acid catalyst may be the solid acid catalyst itself, activated alumina or activated carbon. For example, it may be adsorbed by one or more other adsorbents.
  • a solid acid catalyst is used in combination with a transition metal oxide-supported activated carbon or other adsorbent in a flow-through device, a solid acid catalyst is installed upstream and a transition metal oxide-supported activated carbon or adsorbent is installed downstream, and the solid By acid catalyst
  • a method in which the reaction product is removed with a downstream transition metal oxide-supported activated carbon or an adsorbent is preferred.
  • the sulfur compound heavy by the solid acid catalyst may be removed by fractional distillation.
  • the adsorbent preferably removes a small amount of adsorbed moisture in advance as a pretreatment of the adsorbent. If water is adsorbed, not only does the adsorption of sulfur compounds be hindered, but also the water desorbed from the adsorbent immediately after the introduction of the hydrocarbon is mixed into the hydrocarbon.
  • the zeolite is preferably dried at 130 to 500 ° C, preferably at about 350 to 450 ° C. In the case of activated carbon, it is preferable to dry at about 100 to 200 ° C. in an oxidizing atmosphere such as air. If the temperature is higher than 200 ° C., the weight is reduced due to the reaction with oxygen, which is not preferable. On the other hand, under a non-oxidizing atmosphere such as nitrogen, it is possible to dry at about 100 800 ° C. Heat treatment at 400 to 800 ° C is particularly preferable because it removes organic substances and oxygen contained and improves adsorption performance.
  • the activated carbon supporting a transition metal oxide can be desorbed and regenerated because physical adsorption is mainly performed. Adsorption After desulfurization, the adsorbent can be easily desorbed and regenerated by washing with a solvent, heating under a nitrogen atmosphere, heating under reduced pressure, etc., and can be used repeatedly. In particular, by heating under a non-oxidizing atmosphere (usually under a nitrogen atmosphere) and / or under reduced pressure, sufficient regeneration can be achieved in a short time.
  • Thiophenes are heterocyclic compounds containing one or more sulfur atoms as a heteroatom, in which the heterocyclic ring is a penta- or six-atom ring and has an aromatic property (a double bond is added to the heterocyclic ring to form a double bond). And a sulfur compound in which the heterocyclic ring is not condensed with a benzene ring and derivatives thereof. Also includes compounds in which heterocycles are fused.
  • Thiophene also called thiofuran, is a sulfur compound with a molecular weight of 84.1, represented by the molecular formula CHS.
  • Other representative representative of sulfur atoms represented by the molecular formula CHS.
  • Methylthiophene (thiotrene, molecular formula CHS, molecular weight 98.2), thia
  • dichenylmethane molecular formula CHS, molecular weight 180
  • derivatives thereof dichenylmethane
  • Benzothiophenes are heterocyclic compounds containing one or more sulfur atoms as hetero atoms.
  • the heterocyclic ring is a 5- or 6-atom ring and has an aromatic property (a double bond
  • Benzothiophene also known as thionaphthene or thiocumarone, is a sulfur compound having a molecular weight of 134 and represented by the molecular formula CHS.
  • Other typical benzothiophene also known as thionaphthene or thiocumarone, is a sulfur compound having a molecular weight of 134 and represented by the molecular formula CHS.
  • Other typical benzothiophene also known as thionaphthene or thiocumarone
  • Dibenzothiophenes are heterocyclic compounds containing at least one sulfur atom as a heteroatom, in which the heterocyclic ring is a penta- or six-atom ring and has an aromatic property (a double bond is attached to the heterocyclic ring by two or more). And a sulfur compound in which a heterocyclic ring is condensed with two benzene rings, and a derivative thereof.
  • Dibenzothiophene also known as diphenylene sulfide, biphenylene sulfide, or diphenylene sulfide, can be represented by the molecular formula CHS and has a molecular weight of 184.
  • 4-Methyldibenzothiophene and 4,6-dimethyldibenzothiophene are well known as hard-to-desulfurize compounds in hydrorefining.
  • Other representative dibenzothiophenes include trimethyldibenzothiophene, tetramethyldibenzothiophene, pentamethyldibenzothiophene, hexamethyldibenzothiophene, heptamethinoresinbenzothiophene, otatamethyldibenzothiophene, methyl Ethyldibenzothiophene, dimethylethyldibenzothiophene, trimethylethyldibenzothiophene, Tramethylethyl dibenzothiophene, pentamethylethyl dibenzothiophene, hexamethylethyl dibenzothiophene, heptamethylethyl dibenzothiophene,
  • Methane sulfide molecular formula CHS, molecular weight 198) and derivatives thereof.
  • Both thiophenes and benzothiophenes have a heterocyclic ring containing a sulfur atom as a heteroatom, and in the presence of a solid acid catalyst having high reactivity, cleavage of the heterocyclic ring ⁇ reaction or decomposition of the heterocyclic ring with the aromatic ring. It happens easily.
  • Dibenzothiophenes have lower reactivity than thiophenes and benzothiophenes because benzene rings are bonded to both sides of the thiophene ring. Therefore, solid acid catalysts are more effective in desulfurizing hydrocarbon oils free of dibenzothiophenes, for example, kerosene free of dibenzothiophenes.
  • kerosene having a dibenzothiophene concentration of 0.1 ppm or less as sulfur, preferably 0.1 ppm or less, and more preferably 0.1 ppm or less is desulfurized by a desulfurization method using a solid acid catalyst, the sulfur content is extremely low. It can be reduced to a concentration. Therefore, in a fuel cell system that generates hydrogen for a fuel cell from hydrocarbon oil, the reforming catalyst that extremely dislikes sulfur is not adversely affected, so that the desulfurization method of the present invention is particularly preferably used for a fuel cell system. Can be.
  • HSZ-320NAA Comparative Example
  • KL-type zeolite (HSZ-550KOA (Comparative Example 2-3) manufactured by Tosoh Corporation: SiO / AlO ratio 6.1 mol / mol
  • the NaY-type zeolite, NaX-type zeolite, KL-type zeolite, Na-mordenite, and K-ferrierite of Comparative Example 2_1-5 are generally not acidic catalysts but acidic weak (or no) adsorbents.
  • Example 3 [0049] To 4.0 g of 2-methylthiophene (special grade of reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) diluted to 10% by mass with a toluene solvent (special grade of reagent, manufactured by Junsei Chemical Co., Ltd.) was dried at 400 ° C for 3 hours. After the catalyst was immersed in l.Og and left at room temperature for 24 hours or more, the adsorption capacity of the adsorbent was measured by analyzing the sulfur compound content before and after immersion by gas chromatography. As the acidic catalyst, three types of H—Y type zeolites (manufactured by Tosoh Corporation) having different Si ⁇ / Al O ratios (
  • HSZ-320HOA (Example 3-1): SiO / Al O ratio 5.5mol / mol
  • H-mordenite (HSZ-640HOA (Example 3-4): Si ⁇ / Al O ratio 18.3 mol / m
  • HSZ-320NAA Comparative Example
  • KL type zeolite (HSZ-550KOA (Comparative Example 3-3), manufactured by Tosoh Corporation: SiO / Al O ratio 6.1mol / mol, K content 7% by mass, Na content Rate 0.2
  • Acidic catalyst dried at 400 ° C for 3 hours in 4.0 g of benzothiophene (reagent grade, Tokyo Chemical Industry Co., Ltd.) diluted to 10% by mass with decane solvent (reagent grade, Junsei Chemical Co., Ltd.) was immersed in l.Og, allowed to stand at room temperature for 24 hours or more, and the adsorption capacity of the adsorbent was measured by analyzing the sulfur compound content before and after immersion by gas chromatography.
  • As the acidic catalyst there are three types of H—Y type zeolites (H
  • SZ- 320HOA (Example 4-1): Si_ ⁇ / A1_rei ratio 5.5MolZmol, Na content 3 wt 0/0,
  • KL-type zeolite (HSZ-550KOA (Comparative Example 4-1) manufactured by Tosoh Corporation: SiO / Al O ratio: 6.1 mol / mol, K content: 7% by mass, Na content: 0.2% by mass) ,ratio
  • Benzothiamine diluted to 10% by mass with toluene solvent (special grade reagent, manufactured by Junsei Chemical Co., Ltd.) Ophen (reagent grade, manufactured by Tokyo Kasei Kogyo Co., Ltd.) is immersed in 4.0 g of an acidic catalyst dried at 400 ° C for 3 hours, left at room temperature for 24 hours or more, and the sulfur compound content before and after immersion is measured.
  • the adsorption capacity of the adsorbent was measured by analyzing with a gas chromatograph.
  • As the acidic catalyst there are three types of H—Y type zeolites (H
  • HSZ-320NAA NaY-type zeolite manufactured by Tosoh Corporation
  • KL type zeolite (HSZ-550KOA (Comparative Example 5-4), manufactured by Tosoh Corporation: SiO / AlO ratio 6.1 mol / mol, K content 7 mass%, Na content Rate 0.2
  • Example 5-1 HY-type zeolite 5.5 46
  • Example 5-2 HY-type zeolite 6.0 78
  • Example 5 - 3 HY zeolite 360 3 Comparative Example 5 -1 NaY-type zeolite 5.5 0
  • Comparative example 5-2 NaX-type zeolite 2.5 13
  • Comparative example 5-3 KL-type zeolite 6.10
  • Comparative example 5-4 Na mordenite 1 8.30
  • Comparative example 5-6 Silica gel-2 Comparative example 5-7
  • Alumina-3 Comparative example 5-8
  • Copper oxide supported alumina-8 Comparative example 5-9
  • Nickel oxide supported alumina-4 Comparative example 5 -1 0
  • Zinc oxide-0 Comparative example 5-1 1 Activated carbon-2
  • H- / 3 zeolite (HSZ-930HOD1A (Example 6-4)): SiO / Al O ratio 2
  • Catalistone earth NK-311 (Comparative Example 6-2), copper content 7.6% by mass, specific surface area 264m 2 / g), nickel oxide-supported alumina (Orient Catalyst NK-392 (Comparative Example 6-3), acid Of two Kkenore content of 50 mass 0/0) and zinc oxide (Orient wire carrier data list ne earth manufactured by NK-301H (Comparative Example 6 - 4), 99 wt% zinc oxide content, similarly, using a specific surface area of 10 m 2 / g) An experiment was conducted.
  • H-zeolite (HSZ-930HOD1A (Example 7-4), manufactured by Co., Ltd.): SiO / AlO ratio 2
  • Catalyst NK-311 (Comparative Example 7-2), copper content 7.6% by mass, specific surface area 264m 2 / g) , Nickel oxide-supported alumina (NK-392 manufactured by Orient Catalyst Co., Ltd. (Comparative Example 7-3), nickel oxide content: 50% by mass) and zinc oxide (NK-301H manufactured by Orient Catalyst Co., Ltd. (Comparative Example 7-4))
  • NK-301H manufactured by Orient Catalyst Co., Ltd.
  • Comparative Example 7-4 The same experiment was conducted using a zinc oxide content of 99% by mass and a specific surface area of 10 m 2 / g).
  • NaX-type zeolite F-9 (Comparative Example 8-1): SiO 2 manufactured by Wako Pure Chemical Industries, Ltd.)
  • An acidic catalyst dried at 400 ° C for 3 hours was immersed in 9.0 g of benzene (pure benzene, manufactured by Nippon Petrochemical Co., Ltd., sulfur content 0.38 mass ppm) for 3 hours, and left at 50 ° C for 5 hours.
  • the adsorption capacity of the adsorbent was measured by analyzing the sulfur content of the sulfur compound before and after immersion by a fuel oxidation-ultraviolet fluorescence method.
  • Examples of the acidic catalyst include H-Y type Zolai MHSZ-330HUA manufactured by Tosoh Corporation (Example 9-1): SiO / K ⁇ ⁇ ratio 6.0 molZmol, Na content 0.2
  • a NaY-type zeolite (HSZ-320NAA (Comparative Example 9-1) manufactured by Tosoh Corporation: SiO / Al 2 O ratio: 5.5 mol / mol, Na content: 8% by mass, specific surface area: 700 m 2 / g)
  • NaX type zeolite manufactured by Wako Pure Chemical Industries, Ltd.
  • F_9 (Comparative Example 9-2): SiO / Al 2 O ratio 2.5 mol)
  • Example 9-5 Mass%, specific surface area 280m 2 Zg), activated alumina F-200 manufactured by Alcoa (Comparative Example 9-14) (specific surface area 350m 2 / g), alumina supported on copper oxide (NK- 311 manufactured by Orient Catalyst) A similar experiment was performed using Example 9-5), a copper content of 7.6% by mass, and a specific surface area of 264 m 2 / g).
  • activated carbon supported on copper oxide (NSR-1 manufactured by Toyo CCI (Example 10-1): 12.7% by mass of copper supported, specific surface area 790 m 2 kg), activated carbon (Darco KB manufactured by Aldrich Example 10-1), a specific surface area of 1,500 m 2 / g) was used.
  • Kerosene manufactured by Japan Energy Corporation, boiling range 158.5-270.0 ° C, 5% distillation point 170.5 ° C 10% distillation point 175.0. C, 20% distillation point 181.5. C, 30% distillation point 188.0. C, 40% distillation point 194.5. C, 50% distillation point 202.5. C, 60% distillation point 211.0. C, 70% distillation point 221.0. C, 80% distillation point 232.0. C, 90% distillation point 245.5. C, 95% distillation point 255.5.
  • Solid superacid catalysts include sulfated zirconia alumina (specific surface area 162m2 / g, pore volume 0.305ml / g, central pore diameter 56.4A, zirconia 59wt%, anoremina 31wt%, sulfur 2.9wt%), tungsten Zirconia acid alumina (specific surface area 101m 2 Zg, pore volume 0.302mlZg, median pore diameter 95.0A, zirconia 53wt%, alumina 25wt%, tungstic acid 20wt%), sulfated alumina (specific surface area 300m 2 Zg, pore volume 0.601 ml / g, a central pore diameter 58 ⁇ 9.alpha, sulfur content 4.0 wt%), the particles of sulfate group tin oxide 'alumina (specific surface area 177m 2 / g, pore volume 0.113 ml / g, a central pore diameter 26.7 a)
  • Example 11 4 g of the same kerosene used in Example 11 was immersed in l.Og of the solid superacid catalyst and left at 10 ° C for 24 hours or more, and the sulfur compound content before and after the immersion was oxidized by combustion-UV fluorescence The sulfur content was analyzed by the method.
  • the same catalyst as in Example 11 was used as the solid superacid catalyst.
  • Example 12-1 Zirconia sulfate group 0.99 93.4
  • Example 12-2 Zirconia tungstate 0.1
  • Example 1 2—3 Sulfate Alumina 0.2 98.6
  • Example 1 2 4 Sulfate Tin Oxide 0.3
  • Example 13
  • Figure 1 shows the change over time in the sulfur content of the kerosene flowing out of the system. It can be seen that the sulfur content has been removed for a long time.
  • GC gas chromatography
  • SCD sulfuruminescence Detector
  • the catalytic function and adsorption of the solid acid catalyst and the activated carbon supporting the transition metal oxide are achieved by utilizing the activated carbon supporting the solid acid catalyst and the Z or transition metal oxide. Utilizing the function, it is possible to efficiently and economically remove not only kerosene and light oil but also particularly sulfur compounds in aromatic hydrocarbon oil. Therefore, it is possible to produce particularly low sulfur content light and light oil, as well as extremely low sulfur content.
  • Aromatic hydrocarbons such as benzenes and naphthalenes can be produced and provided as basic raw materials for various petrochemical products or intermediate raw materials.

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